Scribd
Upload
142 views44 pages

Chemical Thermodynamics Y: David A. Katz

This document provides an overview of chemical thermodynamics, covering topics such as the first and second laws of thermodynamics, spontaneous processes, entropy, and Gibbs free energy. It begins by defining the first law of thermodynamics as the law of conservation of energy. It then discusses spontaneous processes, entropy, reversible and irreversible processes, and how entropy relates to the molecular scale. It concludes by introducing Gibbs free energy.

Uploaded by

theodore_estrada
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
142 views44 pages

Chemical Thermodynamics Y: David A. Katz

This document provides an overview of chemical thermodynamics, covering topics such as the first and second laws of thermodynamics, spontaneous processes, entropy, and Gibbs free energy. It begins by defining the first law of thermodynamics as the law of conservation of energy. It then discusses spontaneous processes, entropy, reversible and irreversible processes, and how entropy relates to the molecular scale. It concludes by introducing Gibbs free energy.

Uploaded by

theodore_estrada
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 44

Chemical Thermodynamics

y
David A. Katz
Department of Chemistry
Pima Community College
Tucson, AZ 85709, USA

First Law of Thermodynamics


The First Law of Thermodynamics
y
was expressed
p
in
the study of thermochemistry. It is commonly known
as the Law Conservation of Energy:

The total energy of the universe is a


constant.
gy cannot be created nor destroyed.
y
Energy
Energy can be converted from one form
to another or transferred from a system
t th
to
the surroundings
di
or vice
i versa.

Spontaneous Processes
Spontaneous processes are
those that
that, once started
started, can
proceed without any outside
intervention.
The term spontaneous has
nothing to do with the time or rate
of the process.
process
In the diagram, when the valve is
opened, the gas in flask B will
spontaneously effuse into flask A,
but once the gas is in both flasks,
it will not spontaneously go back
to one flask

Spontaneous Processes
Diamond is
thermodynamically favored
to convert to graphite, but
not kinetically favored.

P
Paper b
burns a productd t
favored reaction. Also
kineticallyy favored once
reaction is begun.

Spontaneous Processes
Processes that are
spontaneous in one
direction are
nonspontaneous in the
reverse direction.
IIn this
thi example,
l an iiron
nail, in contact with the
air will rust
air,
rust.
To reverse the process
something must be done
to the system.

Spontaneous Processes
Processes that are spontaneous at one
temperature may be nonspontaneous at other
temperatures.
Above 0C it is spontaneous for ice to melt.
Below 0C the reverse process is spontaneous.

Spontaneous Processes
In general, spontaneous reactions are exothermic.
F 2O3(s)
Fe
( ) + 2 Al(
Al(s)) 2 F
Fe(s)
( ) + Al2O3(s)
( )

Hrxn = - 848 kJ

(This is known as the Thermite reaction)

The Thermite Reaction

The thermite reaction was discovered in 1893 and patented in


1895 by German chemist Hans Goldschmidt.
Goldschmidt was originally
g
y interested in p
producing
g very
yp
pure
metals by avoiding the use of carbon in smelting, but he soon
realized the value in welding.
The first commercial application
pp
was the welding
g of tram tracks
in Essen, in 1899.

Reversible Processes
Nicolas Lonard Sadi Carnot (1796
1832)
In an 1824 book Rflexions sur la puissance
p
motrice du feu ("Reflections on the Motive Power
of Fire"), he discussed the relation between heat
and mechanical energy and presented an
idealized steam engine that could be used to
understand and clarify the fundamental principles
that are of general applicability to all heat
engines,
i
iindependent
d
d t off th
the particular
ti l d
design
i
choices that might be made.

Reversible Processes
In Carnots idealized engine, a gas is allowed to expand to do
g heat in the process,
p
, and is expanded
p
again
g
without
work,, absorbing
transfer of heat but with a temperature drop. The gas is then
compressed, heat being given off, and finally it is returned to its
original condition by another compression, accompanied by a rise
in temperature
temperature.
This series of operations is known as Carnot's cycle.
It shows that even under ideal conditions a heat engine cannot
convert into mechanical energy all the heat energy supplied to it;
some of the heat energy must be rejected.
Carnots statement lead to the second law of thermodynamics.
An animation of the Carnot Cycle by Michael Fowler and Jacquie Hui Wan Ching,
Department of Physics, University of Virginia can be found at
http://galileoandeinstein.physics.virginia.edu/more_stuff/flashlets/carnot.htm

Reversible Processes
In a reversible
process the system
changes in such a
way that the system
and surroundings
g can
be put back in their
original states by
exactly reversing the
process.

Irreversible Processes

Irreversible processes cannot be undone by


exactly reversing the change to the system.
Spontaneous processes are irreversible.
y
can onlyy be reversed by
y doing
g
This system
work on it.

Entropy
Entropy (S) is a term coined by
R d l h Cl
Rudolph
Clausius
i (1822
(1822-1888)
1888)
In an 1850 paper, On the mechanical
theory of heat
heat, he stated:
the equivalent of the work done by heat is
found in the mere transfer of heat from a
h tt to
hotter
t a colder
ld body,
b d while
hil th
the quantity
tit
of heat remains undiminished.

This is the basic idea of the Second


Law of Thermodynamics.

Entropy
In an 1865 paper, Clausius introduced the concept of
entropy.
entropy
q
The modern form of his equation is S

If we wish to designate S by a proper name we can say of it that it is


the transformation content of the body, in the same way that we say of
the quantity U that it is the heat and work content of the body.
However, since I think it is better to take the names of such quantities
as these, , from the ancient languages, , I proposed to name the
magnitude S the entropy of the body, from the Greek word , a
transformation I have intentionally formed the word entropyso as to be
transformation.
as similar as possible to the word energy, since both these quantities,
which are to be known by these names, are so nearly related to each
other in their physical significance that a certain similarity in their
names seemed to me advantageous.

Entropy
Entropy can be thought of as a measure
of the randomness of a system.
y
It is related to the various modes of
motion in molecules.

Entropy
Like total energy, E, and enthalpy, H,
entropy
py is a state function.
Therefore,
S = Sfinal Sinitial
Standard entropy values in J/mol-K can be found in a table of
thermodynamic values in the appendix of most textbooks

Entropy
For a process occurring at constant
temperature (an isothermal process), the
change in entropy is equal to the heat that
would be transferred if the process were
reversible divided by the temperature:

qrev
S =
T

Second Law of Thermodynamics


The second law of thermodynamics
states that the entropy
py of the universe
increases for spontaneous processes,
and the entropy
py of the universe does
not change for reversible processes.

Second Law of Thermodynamics


In other words:
For reversible processes:

Suniv = Ssystem + Ssurroundings = 0


For irreversible processes:
p

Suniv = Ssystem + Ssurroundings > 0


To summarize:
as a result of all spontaneous processes the
entropy of the universe increases.

Entropy on the Molecular Scale


Ludwig Boltzmann (1844-1906) described
the concept of entropy on the molecular
level.
Temperature
p
is a measure of the average
g
kinetic energy of the molecules in a
sample.

An animation of the Maxwell-Boltzman distribution for molecular speeds in a gas can be


found at
http://www.chm.davidson.edu/chemistryapplets/KineticMolecularTheory/Maxwell.html

Entropy on the Molecular Scale


Molecules exhibit several types of motion:
Translational: Movement of the entire molecule from
one place to another.
Vibrational: Periodic motion of atoms within a molecule.
molecule
Rotational: Rotation of the molecule on about an axis or
rotation about bonds.

Entropy on the Molecular Scale


Boltzmann envisioned the motions of a sample of
molecules
l
l att a particular
ti l iinstant
t t iin titime.
This would be akin to taking a snapshot of all the
molecules.
molecules

He referred to this sampling as a microstate of the


thermodynamic system.

Entropy on the Molecular Scale


Each thermodynamic state has a specific number of
microstates,
i
t t
W associated
W,
i t d with
ith it
it.
Entropy is
S = k lnW
where k is the Boltzmann constant, 1.38 1023 J/K.

Entropy on the Molecular Scale


The change in entropy for a process,
then,, is
S = k lnWfinal k lnWinitial
lnWfinal
S = k ln
lnWinitial
Entropy increases with the number of
microstates in the system.

Entropy on the Molecular Scale


The number of microstates and
and,
therefore, the entropy tends to increase
with increases in
Temperature.
Volume.
Volume
The number of independently moving
molecules.
molecules

Entropy and Physical States


Entropy increases with the freedom
off motion
ti off molecules.
l
l
Ice: vibrational motion only
Water: vibrational, rotational, and limited
translational motion
Water vapor: vibrational, rotational,
and translational motion

Therefore,,
S(g) > S(l) > S(s)

Solutions
Generally, when
a solid is
dissolved in a
solvent,, entropy
py
increases.

Entropy Changes
In general, entropy
increases when
Gases are formed from
liquids and solids.
Liquids or solutions are
formed from solids.
The number of gas
g
molecules increases.
The number of moles
increases.
increases

Third Law of Thermodynamics


The entropy of a pure crystalline substance
at absolute zero is 0.

Standard Entropies
These are molar entropy
values of substances in
their
h i standard
d d states.
Standard entropies tend to
i
increase
with
ith iincreasing
i
molar mass.

Standard Entropies
Larger
g and more complex
p
molecules have
greater entropies.

The number of degrees of freedom increases with


increasing number of atoms which also means
increasing microstates.

Entropy Changes
Entropy changes for a reaction can be
estimated in a manner analogous to that by
which H is estimated:
S = nS(products) - mS(reactants)
where n and m are the coefficients in the
balanced chemical equation
equation.

Entropy Changes in Surroundings


Heat that flows into or out of the
system changes the entropy of the
surroundings.
surroundings
For an isothermal process:
Ssurr =

qsys
T

At constant pressure, qsys is simply


H for the system.

Entropy Change in the Universe


The universe is composed of the system
and the surroundings.
Therefore,
Suniverse = Ssystem + Ssurroundings
For spontaneous processes
Suniverse > 0

Entropy Change in the Universe


This becomes:
Hsystem
Suniverse = Ssystem +
T
Multiplying
M
lti l i b
both
th sides
id b
by T,
T
TSuniverse = Hsystem TSsystem

Gibbs Free Energy


Josiah Willard Gibbs (1839-1903)
Gibbs
Gibb ffree energy, originally
i i ll called
ll d
available energy, was developed in 1873,
in a footnote, Gibbs defined what he called
the available energy of a body as such:
The greatest amount of mechanical work
which can be obtained from a given quantity of
a certain substance in a given initial state,
without increasing its total volume or allowing
heat to p
pass to or from external bodies, except
p
such as at the close of the processes are left in
their initial condition.

Gibbs Free Energy


In the equation

TSuniverse = Hsystem TSsystem


TSuniverse is defined as the Gibbs free
energy, G
G = H TS
When S is positive, G is negative.
Therefore, when G is negative, a process is
spontaneous.

Gibbs Free Energy


In the equation
TSuniverse = Hsystem TSsystem
TSuniverse is defined as the Gibbs free energy, G.
Wh S
When
Suniverse is
i positive,
ii
G
G is
i negative.
i
Therefore, when G is negative, a process is
spontaneous.

Gibbs Free Energy


1 If G is negative
1.
negative, the
forward reaction is
spontaneous.
p
2. If G is 0, the system
is at equilibrium.
q
3. If G is positive, the
reaction is
spontaneous in the
reverse direction.

Standard Free Energy Changes


Analogous to standard enthalpies of
formation are standard free energies
g
of
formation, G.
f (usually given at 298 K)
G = nGf (products) mGf (reactants)
where n and m are the stoichiometric
coefficients.
coefficients

Free Energy and Temperature


At temperatures other than 298 K (25C)
(25 C),

G = H TS
There are two parts to the free energy equation:
H = the enthalpy term
TS = the entropy term
The temperature dependence of free energy,
comes from the entropy
py term.

Free Energy and Temperature

Free Energy and Equilibrium


Under any conditions, standard or nonstandard,
the free energy change can be found using:

G = G
G + RT lnQ
where Q is the reaction quotient
R = the ideal gas constant
constant, 8
8.314
314 J/mol-K
Under standard conditions,, all concentrations are 1 M,,
so Q = 1 and lnQ = 0; the last term drops out and

G = G
G

Free Energy and Equilibrium


At equilibrium
equilibrium, Q = K,
K and G = 0.
0
The equation becomes
0 = G + RT lnK
Rearranging,
g g, this becomes
G = RT lnK
or,
or
K = eG/RT

You might also like